Fluorophenylborates and their use as activators in catalyst systems for olefin polymerization

ABSTRACT

A fluorophenylborate useful as an activator for an olefin polymerization catalyst is represented by the formula: 
 
Ct + [B—(Ar f R n ) 4 ] − 
 
where Ct +  is a cation capable of extracting an alkyl group from, or breaking a carbon-metal bond of, an organo metallic compound; Ar f  is a fluorophenyl group; n is 1 or 2; and each R is independently selected from a fluorophenyl group and a fluoronaphthyl group, provided that when n=1, each R group is connected at the 3-position relative the connection between the associated Ar f  group and the boron atom and, when n=2; the R groups are connected at the 3-position and the 5-position respectively relative the connection between the associated Ar f  group and the boron atom.

FIELD

This invention relates to novel fluorophenylborates and their use asactivators in catalyst systems for olefin polymerization.

BACKGROUND

Many catalyst systems for polymerizing olefins, including metalloceneand Ziegler-Natta catalyst systems, include an activator or co-catalystto increase the rate at which the primary catalyst, for example themetallocene complex, polymerizes olefin monomers. An activator may alsoaffect the molecular weight, degree of branching, comonomer content andother properties of the resultant polymer. Typical activators include,for example, alumoxanes, aluminum alkyls and ionizing activators.

Ionizing activators generally include a cation capable of abstracting analkyl group, or breaking a carbon-metal bond, from the organometallicprimary catalyst species together with a charge-balancingnoncoordinating or weakly coordinating anion. One known class ofionizing activator are fluorophenylborates and, in particular,perfluorophenylborates, the use of which are reviewed by Eugene at al.in Chem. Rev. 2000, 100, page 1391.

Recently, a variety of researchers have investigated the effect ofsubstituting the fluorine atoms in fluorophenylborates, particularly atthe para-position relative to the boron atom, with bulky groups with aview to increasing the solubility of the activator in the aliphaticsolvents typically used in solution polymerization processes and toincreasing the molecular weight of the resultant polymers. For example,in J. Am. Chem. Soc. 1998, 120, page 6287, Chen et al. disclosesubstituting the para fluorine with a —Si(t-Bu)₂Me group or —Si(i-Pr)₃group, whereas substitution, again at the para-position, with an—OSi(i-Pr)₃ group is proposed in U.S. Pat. No. 6,541,410. InternationalPatent Publication No. WO 01/81435 discloses para-substitution with an—N(R)(C₆F₅) moiety, where R can be methyl, whereas para-substitutionwith a —C₆F₅ moiety is proposed in Japanese Published Patent ApplicationNo. 9-15892 and with a —CF(C₆F₅)₂ moiety is proposed in J. Am. Chem.Soc. 2000, 122, page 1832.

To date, however, little or no attention has been paid to substitutionat the meta positions on the phenyl groups of fluorophenylborates.

SUMMARY

Accordingly, the invention resides in one aspect in a fluorophenylborateuseful as an activator for an olefin polymerization catalyst, thefluorophenylborate being represented by the formula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻where Ct⁺ is a cation capable of extracting an alkyl group from, orbreaking a carbon-metal bond of, an organo metallic compound; Ar^(f) isa fluorophenyl group; n is 1 or 2; and each R is independently selectedfrom a fluorophenyl group and a fluoronaphthyl group, provided that whenn=1, each R group is connected at the 3-position relative the connectionbetween the associated Ar^(f) group and the boron atom and, when n=2;the R groups are connected at the 3-position and the 5-positionrespectively relative the connection between the associated Ar^(f) groupand the boron atom.

Conveniently, each R is independently selected from a perfluorophenylgroup and a perfluoronaphthyl group.

In one embodiment, each Ar^(f) is a perfluorophenyl group.

Conveniently, Ct⁺ is selected from silylium, trityl carbenium, Group-12metal, anilinium, ammonium, phosphonium, and arsonium cations, andanilinium, ammonium, phosphonium, and arsonium cationic derivativeswherein the cationic derivatives contain C₁ to C₈ hydrocarbyl,hydrocarbylsilyl, or hydrocarbyl-amine substituents for one or morecation hydrogen atoms. In one preferred embodiment, Ct⁺ is a[4-t-butyl-N,N-dimethylanilinium] cation.

In a further aspect, the invention resides in an olefin polymerizationcatalyst system comprising (a) a catalyst precursor comprising anorganometallic compound and (b) an activator comprising a compoundrepresented by the formula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻where Ct⁺ is a cation capable of extracting an alkyl group from, orbreaking a carbon-metal bond of, an organo metallic compound; Ar^(f) isa fluorophenyl group; n is 1 or 2; and each R is independently selectedfrom a fluorophenyl group and a fluoronaphthyl group, provided that whenn=1, each R group is connected at the 3-position relative the connectionbetween the associated Ar^(f) group and the boron atom and, when n=2;the R groups are connected at the 3-position and the 5-positionrespectively relative the connection between the associated Ar^(f) groupand the boron atom.

Conveniently, said catalyst precursor is selected from a metallocenecatalyst precursor, a bisamide catalyst precursor, an amine bisamidecatalyst precursor, or a pyridine bisamide catalyst precursor.

In yet a further aspect, the invention resides in a process forpolymerizing at least one olefin monomer in the presence of a catalystsystem according to said further aspect of the invention.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, when apolymer is referred to as comprising a monomer, the monomer present inthe polymer is the polymerized form of the monomer. Likewise whencatalyst components are described as comprising neutral stable forms ofthe components, it is well understood by one of ordinary skill in theart, that the active form of the component is the form that reacts withthe monomers to produce polymers. In addition, a reactor is anycontainer(s) in which a chemical reaction occurs.

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inCHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

The term “catalyst system” is defined to mean a catalystprecursor/activator pair. When “catalyst system” is used to describesuch a pair before activation, it means the unactivated catalyst(precatalyst) together with an activator and, optionally, aco-activator. When it is used to describe such a pair after activation,it means the activated catalyst and the activator or othercharge-balancing moiety.

The term “catalyst precursor” is also often referred to as precatalyst,catalyst, catalyst precursor, catalyst compound, transition metalcompound, metallocene complex, and/or transition metal complex. Thesewords are used interchangeably. Activator and cocatalyst are also usedinterchangeably. A scavenger is a compound that is typically added tofacilitate oligomerization or polymerization by scavenging impurities.Some scavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments a co-activator can be pre-mixed with the transitionmetal compound to form an alkylated transition metal compound. Thetransition metal compound may be neutral as in a precatalyst, or acharged species with a counterion as in an activated catalyst system.

For purposes of this disclosure, the term “fluorophenyl group” means aphenyl group in which at least one hydrogen atom has been replaced byfluorine and is intended to include phenyl compounds in which otherhydrogen atoms on the aromatic ring have been replaced by othersubstituents, such as a hydrocarbyl substituent. The term“perfluorophenyl group” means that each phenyl hydrogen atom has beenreplaced by a fluorine atom except, in the case of the Ar^(f) group, theor each hydrogen atom that has been replaced by an R group.

Similarly, the term “fluoronaphthyl group” means a naphthyl group inwhich at least one hydrogen atom has been replaced by fluorine and isintended to include naphthyl compounds in which other hydrogen atoms onthe aromatic ring have been replaced by other substituents, such as ahydrocarbyl substituent. The term “perfluoronaphthyl group” means thateach naphthyl hydrogen atom has been replaced by a fluorine atom.

The terms “hydrocarbyl radical”, “hydrocarbyl” and “hydrocarbyl group”are defined to include any radical that contains carbon and hydrogen andmay be linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic, and include a substituted hydrocarbyl radical, as thisterm is defined below. When referring to a hydrogen substitutent, theterms “hydrogen” and “hydrogen radical” are used interchangeably.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic ringstructure.

In some embodiments, the hydrocarbyl radical is selected from methyl,ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl,octyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl propynyl,butynyl, pentynyl, hexynyl, heptynyl, octynyl, butadienyl, pentadienyl,hexadienyl, heptadienyl and octadienyl.

Also included are isomers of saturated, partially unsaturated andaromatic cyclic and polycyclic structures wherein the hydrocarbylradical may additionally be subjected to the types of substitutionsdescribed above. Examples include phenyl, methylphenyl, dimethylphenyl,ethylphenyl, benzyl, methylbenzyl, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl,norbornyl, norbornenyl, adamantyl and the like.

For this disclosure, when a radical is listed, it indicates that radicaltype and all other radicals formed when that radical type is subjectedto the substitutions defined above. Alkyl, alkenyl and alkynyl radicalslisted include all isomers including, where appropriate, cyclic isomers.For example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compound having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-methyldiphenyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

The term “hydrocarbylsilyl” is used herein to refer to any branched orunbranched, saturated or unsaturated acyclic or acyclic hydrocarbonradical which has 1 to 8 carbon atoms and which has one or more hydrogenatoms replaced by a silicon atom.

The term “hydrocarbyl-amine” is used herein to refer to any branched orunbranched, saturated or unsaturated acyclic or acyclic hydrocarbonradical has one or more hydrogen atoms replaced by an amino group orsubstituted amino group.

Fluorophenylborate Activator

The present invention provides a novel fluorophenylborate useful as anactivator for an olefin polymerization catalyst system and having theformula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻where Ct⁺ is a cation capable of extracting an alkyl group from, orbreaking a carbon-metal bond of, an organo metallic compound; Ar^(f) isa fluorophenyl group; n is 1 or 2; and each R is independently selectedfrom a fluorophenyl group and a fluoronaphthyl group, provided that whenn=1, each R group is connected at the 3-position relative the connectionbetween the associated Ar^(f) group and the boron atom and, when n=2;the R groups are connected at the 3-position and the 5-positionrespectively relative the connection between the associated Ar^(f) groupand the boron atom.

Conveniently, each R is independently selected from a perfluorophenylgroup and a perfluoronaphthyl group and each Ar^(f) is a perfluorophenylgroup.

Representative compounds according to the invention therefore includethe anions:

Conveniently, Ct⁺ is selected from silylium, trityl carbenium, Group-12metal, anilinium, ammonium, phosphonium, and arsonium cations, andanilinium, ammonium, phosphonium, and arsonium cationic derivativeswherein the cationic derivatives contain C₁ to C₈ hydrocarbyl,hydrocarbylsilyl, or hydrocarbyl-amine substituents for one or morecation hydrogen atoms. In one preferred embodiment, Ct⁺ is a[4-t-butyl-N,N-dimethylanilinium] cation (abbreviated herein as DMAH).

Method of Synthesizing the Fluorophenylborate Activator

The fluorophenylborate of the invention may be prepared by syntheticmethods well known in the art. For example, when n=1 and each of R andAr^(f) is a perfluorophenyl group, one of the bromide substituents incommercially available 1,3-dibromotetrafluorobenzene can readily bereplaced by hydrogen by the sequential addition of one equivalent ofEtMgBr, followed by an aqueous hydrochloric acid quench. The resulting3-bromotetrafluorobenzene can then be used to produce3-pentafluorophenyl-2,4,5,6-tetrafluorobenzene via a copper mediatedcoupling reaction using, for example, (C₆F₅)₂Cu in dioxane, see Sakamotoet al. J. Am. Chem. Soc. 2000, 122, page 1832. The resulting biphenylcan then be converted to the corresponding anilinium borate usingstandard techniques.

When n=2 and each of R and Ar^(f) is a perfluorophenyl group, synthesiscan readily be achieved by initially brominating commercially available1,3,5-trifluorobenzene to produce the correspondingtrifluorotribromobenzene. One of the bromide substituents in theresulting trifluorotribromobenzene can then be replaced by hydrogen bythe sequential addition of one equivalent of EtMgBr, followed by anaqueous hydrochloric acid quench. The resulting3,5-dibromotrifluorobenzene can then used to make3,5-bis(pentafluorophenyl)trifluorobenzene via a copper mediatedcoupling reaction. The resultant triphenyl can then be brominated toproduce 3,5-bis(pentafluorophenyl)-1-bromotrifluorobenzene, which canthen be converted to the corresponding anilinium borate using standardtechniques.

Olefin Polymerization Catalyst System

The fluorophenylborate of the invention according to the invention isparticularly useful as part of a catalyst system for polymerizingolefins. In such a catalyst system the fluorophenylborate is combinedwith an organometallic catalyst precursor to perform as an activator toincrease the rate at which the catalyst precursor polymerizes olefinmonomers and/or to affect the molecular weight, degree of branching,comonomer content or other properties of the resultant polymer.

Organometallic precursors compounds suitable for use with thefluorophenylborate activator of the invention include the knownorganometallic, transition metal compounds useful in traditionalZiegler-Natta coordination polymerization, particularly the metallocenecompounds known to be useful in coordination polymerization. These willtypically include Group 3-10 transition metal compounds wherein at leastone metal ligand can be abstracted by the cocatalyst activator,particularly those ligands including hydride, hydrocarbyl, andhydrocarbylsilyl, and lower alkyl-substituted (C₁ to C₁₀) derivativesthereof. Examples include hydride, methyl, benzyl, dimethyl-butadiene,etc. Ligands capable of being abstracted and transition metal compoundscomprising them include those metallocenes described in, for exampleU.S. Pat. No. 5,198,401 and International Patent Publication No. WO92/00333. Additionally, where the metal ligands include halogen, amidoor alkoxy labile ligands (for example, biscyclopentadienyl zirconiumdichloride) which do not allow for ready abstraction with the activatingcocatalysts of the invention, they can be converted into suitableligands via known alkylation reactions with organometallic compoundssuch as lithium or aluminum hydrides or alkyls, alkylalumoxanes,Grignard reagents, etc. See EP 0 500 944 and EP 0 570 982 for thereaction of organoaluminum compounds with dihalo-substituted metallocenecompounds prior to addition of activating anion compounds.

Further description of metallocene compounds which comprise, or can bealkylated to comprise, at least one ligand capable of abstraction toform a catalytically active transition metal cation appear in the patentliterature, e.g., EP-A-0 129 368, U.S. Pat. Nos. 4,871,705, 4,937,299,5,324,800, 5,470,993, 5,491,246, 5,512,693, EP-A-0 418 044, EP-A-0 591756 and International Patent Publication Nos. WO 92/00333, WO 94/01471and WO 97/22635. Generally, such metallocene compounds comprise mono- orbiscyclopentadienyl substituted Group 3, 4, 5, or 6 transition metalcompounds wherein the ancillary ligands may be themselves substitutedwith one or more groups and may be bridged to each other, or may bebridged through a heteroatom to the transition metal. Preferably thecyclopentadienyl rings (including substituted cyclopentadienyl-basedfused ring systems, such as indenyl, fluorenyl, azulenyl, or substitutedanalogs of them), when bridged to each other, will be loweralkyl-substituted (C₁ to C₆) in the 2 position (with or without asimilar 4-position substituent in the fused ring systems) and mayadditionally comprise alkyl, cycloalkyl, aryl, alkylaryl and orarylalkyl substituents, the latter as linear, branched or cyclicstructures including multi-ring structures, for example, those of U.S.Pat. Nos. 5,278,264 and 5,304,614. Such substituents should each haveessentially hydrocarbyl characteristics and will typically contain up to30 carbon atoms but may be heteroatom containing with 1-5non-hydrogen/carbon atoms, e.g., N, S, O, P, Ge, B and Si.

Metallocene compounds suitable for the preparation of linearpolyethylene or ethylene-containing copolymers (where copolymer meanscomprising at least two different monomers) are essentially any of thoseknown in the art, see International Patent Publication No. WO 92/00333and U.S. Pat. Nos. 5,001,205, 5,198,401, 5,324,800, 5,304,614 and5,308,816, for specific listings. Selection of metallocene compounds foruse to make isotactic or syndiotactic polypropylene, and theirsyntheses, are well-known in the art, specific reference may be made toboth patent and academic literature, see for example Journal ofOrganometallic Chemistry 369, 359-370 (1989). Typically those catalystsare stereorigid asymmetric, chiral or bridged chiral metallocenes. See,for example, U.S. Pat. Nos. 4,892,851, 5,017,714, 5,296,434, 5,278,264,International Patent Publication No. WO-A-93/19103, EP-A2-0 577 581,EP-A1-0 578 838, Spaleck et al, Organometallics 1994, 13, 954-963, andBrinzinger et al, Organometallics 1994, 13, 964-970, and documentsreferred to therein. Though many of the above are directed to catalystsystems with alumoxane activators, the analogous metallocene compoundswill be useful with the cocatalyst activators of this invention foractive coordination catalyst systems, when the halogen, amide or alkoxycontaining ligands of the metals (where occurring) are replaced withligands capable of abstraction, for example, via an alkylation reactionas described above, and another is a group into which the ethylene groupmay insert, for example, hydride, alkyl, alkenyl, or silyl.

Representative metallocene compounds can have the formula:L^(A)L^(B) L^(C) _(i)MDEwhere, M is a Group 3 to 6 metal; L^(A) is a substituted orunsubstituted cyclopentadienyl or heterocyclopentadienyl ancillaryligand π-bonded to M; L^(B) is a member of the class of ancillaryligands defined for L^(A), or is J, a heteroatom ancillary ligandσ-bonded to M; the L^(A) and L^(B) ligands may be covalently bridgedtogether through one or more Group 13 to 16 element-containing linkinggroups; L^(C) _(i) is an optional neutral, non-oxidizing ligand having adative bond to M (i equals 0 to 3); and, D and E are independentlylabile ligands, each having a metal-carbon bond to M, optionally bridgedto each other or L^(A) or L^(B), which bond can be broken forabstraction purposes by a suitable activator and into which apolymerizable monomer or macromonomer can insert for coordinationpolymerization. Also, the use of hetero-atom containing rings or fusedrings, where a non-carbon Group 13, 14, 15 or 16 atom replaces one ofthe ring carbons is considered for this specification to be within theterms “cyclopentadienyl”, “indenyl”, and “fluorenyl”. See, for example,the International Patent Publication Nos. WO 98/37106 and WO 98/41530.Substituted cyclopentadienyl structures means that one or more hydrogenatoms is replaced with hydrocarbyl, hydrocarbylsilyl, orheteroatom-containing like structures. The hydrocarbyl structuresspecifically include C₁ to C₃₀ linear, branched, cyclic alkyl andcycloaromatic fused and pendent rings. These rings may also besubstituted with similar structures.

Non-limiting representative metallocene compounds includemonocyclopentadienyl compounds such aspentamethylcyclopentadienyltitanium isopropoxide,pentamethylcyclopentadienyltribenzyl titanium,dimethylsilyltetramethylcyclopentadienyl-tert-butylamido titaniumdichloride, pentamethylcyclopentadienyl titanium trimethyl,dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconiumdimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdimethyl, unbridged biscyclopentadienyl compounds such as bis(1,3-butyl,methylcyclopentadienyl)zirconium dimethyl,pentamethylcyclopentadienyl-cyclopentadienyl zirconium dimethyl,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdimethyl; bridged bis-cyclopentadienyl compounds such asdimethylsilylbis(tetrahydroindenyl)zirconium dichloride andsilacyclobutyl(tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl)zirconiumdimethyl; bridged bisindenyl compounds such as dimethylsilylbisindenylzirconium dichloride, dimethylsilylbisindenyl hafnium dimethyl,dimethylsilylbis(2-methylbenzindenyl)zirconium dichloride,dimethylsilylbis(2-methylbenzindenyl)zirconium dimethyl; and fluorenylligand-containing compounds, e.g.,diphenylmethyl(fluorenyl)(cyclopentadienyl)zirconium dimethyl; and theadditional mono- and biscyclopentadienyl compounds such as those listedand described in U.S. Pat. Nos. 5,017,714 and 5,324,800, InternationalPatent Publication No. WO 92/00333 and EP-A-0 591 756.

Representative traditional Ziegler-Natta transition metal compoundsinclude tetrabenzyl zirconium, tetra bis(trimethylsiylmethyl)zirconium,oxotris(trimethlsilylmethyl)vanadium, tetrabenzyl hafnium, tetrabenzyltitanium, bis(hexamethyldisilazido)dimethyl titanium,tris(trimethylsilylmethyl)niobium dichloride,tris(trimethylsilylmethyl)tantalum dichloride. The important features ofsuch compositions for coordination polymerization are the ligand capableof abstraction and that ligand into which the ethylene (olefinic) groupcan be inserted. These features enable ligand abstraction from thetransition metal compound and the concomitant formation of the ioniccatalyst composition of the invention.

Additional organometallic transition metal compounds suitable as olefinpolymerization catalysts in accordance with the invention will be any ofthose Group 3-10 that can be converted by ligand abstraction or σ-bondscission into a catalyticly active cation and stabilized in that activeelectronic state by a noncoordinating or weakly coordinating anionsufficiently labile to be displaced by an olefinically unsaturatedmonomer such as ethylene.

Exemplary compounds include those described in International PatentPublications Nos. WO 96/23010 and WO 97/48735 and Gibson et. al., Chem.Comm., pp. 849-850 (1998), which disclose diimine-based ligands forGroup 8- to 10 metal compounds shown to be suitable for ionic activationand olefin polymerization. See also WO 97/48735. Transition metalpolymerization catalyst systems from Group 5 to 10 metals wherein theactive transition metal center is in a high oxidation state andstabilized by low coordination number polyanionic ancillary ligandsystems are described in U.S. Pat. Nos. 5,502,124 and 5,504,049. Seealso the Group 5 organometallic catalyst compounds of U.S. Pat. No.5,851,945 and the tridentate ligand containing Group 5 to 10organometallic catalyst compounds of U.S. Pat. No. 6,294,495. Group 11catalyst precursor compounds, capable of activation with ionizingcocatalysts, useful for olefins and vinyl group-containing polarmonomers are described and exemplified in International PatentPublication No. WO 99/30822.

U.S. Pat. No. 5,318,935 describes bridged and unbridged bisamidotransition metal catalyst compounds of Group 4 metals capable ofinsertion polymerization of α-olefins. Bridged bis(arylamido) Group 4compounds for olefin polymerization are described by McConville et al inOrganometallics 1995, 14, 5478-5480. Further work appearing inMacromolecules 1996, 29, 5241-5243 describes bridged bis(arylamido)Group 4 compounds that are active catalysts for polymerization of1-hexene. Additional transition metal compounds suitable in accordancewith the invention include those described in International PatentPublication No. WO 96/40805. Cationic Group 3 or Lanthanide metalcomplexes for coordination polymerization of olefins are disclosed inInternational Patent Publication No. WO 00/18808. The precursor metalcompounds are stabilized by a monoanionic bidentate ancillary ligand andtwo monoanionic ligands and are capable of activation with the ioniccocatalysts of the invention.

Additional description of suitable organometallic or organometalloidcatalyst precursor compounds may be found in the literature, any of suchwill be suitable where comprising, or where capable of alkylation tocomprise, ligands capable of ionizing abstraction. See, for instance, V.C. Gibson, et al, “The Search for New-Generation Olefin PolymerizationCatalysts: Life Beyond Metallocenes”, Angew. Chem. Int. Ed, 38, 428-447(1999).

In general, in the catalyst system of the invention the catalystprecursor and the activator are combined in weight ratios of about 10:1to about 1:10; such as about 5:1 to about 1:5; for example about 2:1 toabout 1:2. Multiple activators may be used, including mixtures ofalumoxanes with the fluorophenylborate activator of the invention.Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O—sub-units, where R¹ is an alkyl group. Examples of alumoxanes includemethylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxaneand isobutylalumoxane.

When using the catalyst activator of the invention, the total catalystsystem will generally additionally comprise one or more organometalliccompound scavenging agents. Such compounds are effective for removingpolar impurities from the reaction environment and for increasingcatalyst activity. Impurities can be inadvertently introduced with anyof the polymerization reaction components, particularly with a solvent,monomer and catalyst feed, and adversely affect catalyst activity andstability. The polar impurities, or catalyst poisons, include water,oxygen and metal impurities. Preferably steps are taken to removeimpurities from the polymerization feedstocks before their use, but someminor amounts of organometallic scavenger compound will still normallybe used in the polymerization process itself.

Typically these scavenger compounds will be Group 13 organometalliccompounds, such as those disclosed in U.S. Pat. Nos. 5,153,157 and5,241,025 and International Patent Publication Nos. WO 91/09882, WO94/03506, WO 93/14132 and WO 95/07941. Exemplary compounds includetriethyl aluminum, triethyl borane, triisobutyl aluminum,methylalumoxane, and isobutyl aluminumoxane. Those compounds havingbulky or C₆ to C₂₀ linear hydrocarbyl substituents covalently bound tothe metal or metalloid center are preferred to minimize adverseinteraction with the active catalyst. Examples include triethylaluminum,but more preferably, bulky compounds such as triisobutylaluminum,triisoprenylaluminum, and long-chain linear alkyl-substituted aluminumcompounds, such as tri-n-hexylaluminum, tri-n-octylaluminum, ortri-n-dodecylaluminum.

The catalyst system of this invention may also include a supportmaterial or carrier. For example, a metallocene complex and one or moreactivators may be deposited on, contacted with, vaporized with, bondedto, or incorporated within, adsorbed or absorbed in, or on, one or moresupports or carriers.

The support material may any of the conventional support materials usedin polymerization catalyst systems. Preferably the support material is aporous support material, for example, talc, a zeolite, an inorganicoxide and/or an inorganic chloride. Other support materials includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene divinyl benzenepolyolefins or polymeric compounds, clays, or any other organic orinorganic support material and the like, or mixtures thereof.

The preferred support materials are inorganic oxides that include Group2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, which may or may not be dehydrated, fumed silica, alumina (WO99/60033), silica-alumina and mixtures thereof. Other useful supportsinclude magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No.5,965,477), montmorillonite (European Patent EP-B1 0 511 665),phyllosilicate and the like. Also, combinations of these supportmaterials may be used, for example, silica-chromium, silica-alumina,silica-titania and the like. Additional support materials may includethose porous acrylic polymers described in EP 0 767 184 B1. Othersupport materials include nanocomposites as described in InternationalPatent Publication No. WO 99/47598, aerogels as described inInternational Patent Publication No. WO 99/48605, spherulites asdescribed in U.S. Pat. No. 5,972,510 and polymeric beads as described inInternational Patent Publication No. WO 99/50311.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the carrier useful in the invention typically haspore size in the range of from about 10 to about 1000 Å, preferablyabout 50 to about 500 Å, and most preferably about 75 to about 350 Å.

As is well known in the art, the catalyst components, that is themetallocene complex and the activator, may also be supported together onone inert support, or the components may be independently placed on twoinert supports and subsequently mixed. Of the two methods, the former ispreferred.

In another embodiment the support may comprise one or more types ofsupport material which may be treated differently. For example one coulduse two different silicas that had different pore volumes or had beencalcined at different temperatures. Likewise one could use a silica thathad been treated with a scavenger or other additive and a silica thathad not.

Monomers

The catalyst system described herein may be used for the polymerizationof one or more of monomers. Typical monomers include monomers havingfrom 2 to 30 carbon atoms, preferably 2-12 carbon atoms, and morepreferably 2 to 8 carbon atoms. Useful monomers include linear, branchedor cyclic olefins, especially linear branched or cyclic alpha-olefins;linear, branched or cyclic diolefins, such as linear branched or cyclicalpha-omega olefins; and linear, branched or cyclic polyenes.

Preferred linear alpha-olefins include C₂ to C₈ alpha-olefins, morepreferably ethylene, propylene, 1-butene, 1-hexene, and 1-octene, evenmore preferably ethylene, propylene or 1-butene. Preferred branchedalpha-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene, and3,5,5-trimethyl-1-hexene, 5-ethyl-1-nonene. Preferredaromatic-group-containing monomers contain from 7 up to 30 carbon atoms.Suitable aromatic-group-containing monomers comprise at least onearomatic structure, preferably from one to three, more preferably aphenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C₁ to C₁₀ alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers can also be used. Thesemonomers can contain from 5 up to 30 carbon atoms. Suitable non-aromaticcyclic group containing monomers preferably have at least onepolymerizable olefinic group that is either pendant on the cyclicstructure or is part of the cyclic structure. The cyclic structure mayalso be further substituted by one or more hydrocarbyl groups such as,but not limited to, C₁ to C₁₀ alkyl groups. Preferred non-aromaticcyclic group containing monomers include vinylcyclohexane,vinylcyclohexene, vinylnorbornene, ethylidene norbornene,cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantaneand the like.

Diolefin monomers useful in this invention include any hydrocarbonstructure, preferably C₄ to C₃₀, having at least two unsaturated bonds,wherein at least two of the unsaturated bonds are readily incorporatedinto a polymer by either a stereospecific or a non-stereospecificcatalyst(s). It is further preferred that the diolefin monomers beselected from alpha, omega-diene monomers (i.e. di-vinyl monomers). Morepreferably, the diolefin monomers are linear di-vinyl monomers, mostpreferably those containing from 4 to 30 carbon atoms. Examples ofpreferred dienes include butadiene, pentadiene, hexadiene, heptadiene,octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene,tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene,particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weightpolybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

In a preferred embodiment one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Preferred monomers include one or more of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1,decene-1,3-methyl-pentene-1, norbornene, norbornadiene, vinylnorbornene, ethylidene norbornene monomers.

In a particularly preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.Particularly, the comonomers arebutene-1,4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1,the most preferred being hexene-1, butene-1 and octene-1.

In another preferred embodiment the polymer produced herein is apropylene homopolymer or copolymer. The comonomer is preferably a C₄ toC₂₀ linear, branched or cyclic monomer, and in one embodiment is a C₄ toC₁₂ linear or branched alpha-olefin, preferably butene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and the like. Ethylene may bepresent at 5 mol % or less.

In another embodiment ethylene or propylene is polymerized with at leasttwo different comonomers to form a terpolymer. The preferred comonomersare a combination of alpha-olefin monomers having 4 to 10 carbon atoms,more preferably 4 to 8 carbon atoms, optionally with at least one dienemonomer. The preferred terpolymers include the combinations such asethylene/butene-1/hexene-1, ethylene/propylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/norbornene and the like.

In another embodiment, the olefin polymer comprises:

a first monomer present at from 40 to 95 mole %, preferably 50 to 90mole %, preferably 60 to 80 mole %, and

a comonomer present at from 5 to 40 mole %, preferably 10 to 60 mole %,more preferably 20 to 40 mole %, and

a termonomer present at from 0 to 10 mole %, more preferably from 0.5 to5 mole %, more preferably 1 to 3 mole %.

Typically, the first monomer comprises one or more of any C₃ to C₈linear, branched or cyclic alpha-olefins, including propylene, butene(and all isomers thereof), pentene (and all isomers thereof), hexene(and all isomers thereof), heptene (and all isomers thereof), and octene(and all isomers thereof). Preferred monomers include propylene,1-butene, 1-hexene, 1-octene, and the like.

The comonomer may comprise one or more of any C₂ to C₄₀ linear, branchedor cyclic alpha-olefins (provided ethylene, if present, is present at 5mole % or less), including ethylene, propylene, butene, pentene, hexene,heptene, and octene, nonene, decene, undecene, dodecene, hexadecene,styrene, 3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,norbornene and cyclopentene.

The termonomer may comprise one or more of any C₂ to C₄₀ linear,branched or cyclic alpha-olefins, (provided ethylene, if present, ispresent at 5 mole % or less), including, but not limited to, ethylene,propylene, butene, pentene, hexene, heptene, and octene, nonene, decene,undecene, dodecene, hexadecene, butadiene, 1,5-hexadiene,1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,11-dodecadiene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1, andcyclopentadiene.

Polymerization Process

The catalyst systems described above are suitable for use in a solution,bulk, gas or slurry polymerization process or a combination thereof,preferably solution phase or bulk phase polymerization process.

One or more reactors in series or in parallel may be used in thepolymerization process. Catalyst component and activator may bedelivered as a solution or slurry, either separately to the reactor,activated in-line just prior to the reactor, or preactivated and pumpedas an activated solution or slurry to the reactor. A preferred operationis two solutions activated in-line. For more information on methods tointroduce multiple catalysts into reactors, see U.S. Pat. No. 6,399,722and International Patent Publication No. WO 01/30862. While thesereferences may emphasize gas phase reactors, the techniques describedare equally applicable to other types of reactors, including continuousstirred tank reactors, slurry loop reactors and the like.Polymerizations are carried out in either single reactor operation, inwhich monomer, comonomers, catalyst/activator, scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors.

In one embodiment 500 ppm or less of hydrogen is added to thepolymerization, or 400 ppm or less, or 300 ppm or less. In otherembodiments at least 50 ppm of hydrogen is added to the polymerization,or 100 ppm or more, or 150 ppm or more.

Gas Phase Polymerization

Generally, a fluidized gas bed process is used for producing polymers,with a gaseous stream containing one or more monomers being continuouslycycled through the fluidized bed in the presence of a catalyst underreactive conditions. The gaseous stream is withdrawn from the fluidizedbed and recycled back into the reactor. Simultaneously, polymer productis withdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661 and 5,668,228.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique useful in theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179. The preferredtemperature in the particle form process is within the range of about85° C. to about 110° C. Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control.

The reactor is maintained at a pressure of 3620 kPa to 4309 kPa and at atemperature in the range of about 60° C. to about 104° C. depending onthe desired polymer melting characterisitcs. Reaction heat is removedthrough the loop wall since much of the reactor is in the form of adouble-jacketed pipe. The slurry is allowed to exit the reactor atregular intervals or continuously to a heated low pressure flash vessel,rotary dryer and a nitrogen purge column in sequence for removal of theisobutane diluent and all unreacted monomer and comonomers. Theresulting hydrocarbon free powder is then compounded for use in variousapplications.

In one embodiment of the slurry process useful in the invention theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 to about 10 weight percent, preferably fromabout 2 to about 7 weight percent, more preferably from about 2.5 toabout 6 weight percent, most preferably from about 3 to about 6 weightpercent.

Another process useful in the invention is where the process, preferablya slurry process is operated in the absence of or essentially free ofany scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described inInternational Patent Publication No. WO 96/08520 and U.S. Pat. No.5,712,352.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum and anexcess of alumoxane or modified alumoxane.

Homgeneous, Bulk, or Solution Phase Polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization with reactor cooling by reactor jackets or cooling coilsto cool the contents of the reactor, auto refrigeration, pre-chilledfeeds, vaporization of liquid medium (diluent, monomers or solvent) orcombinations of all three. Adiabatic reactors with pre-chilled feeds mayalso be used. The reactor temperature depends on the catalyst used. Ingeneral, the reactor temperature preferably can vary between about 30°C. and about 160° C., more preferably from about 90° C. to about 150°C., and most preferably from about 100° C. to about 140° C.Polymerization temperature may vary depending on catalyst choice. Forexample a diimine Ni catalyst may be used at 40° C., while a metalloceneTi catalyst can be used at 100° C. or more. In series operation, thesecond reactor temperature is preferably higher than the first reactortemperature. In parallel reactor operation, the temperatures of the tworeactors are independent. The pressure can vary from about 1 mm Hg to2500 bar (25,000 MPa), preferably from 0.1 bar to 1600 bar (1-16,000MPa), most preferably from 1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor or plug flow reactor, or more than one reactor operated inseries or parallel. These reactors may have or may not have internalcooling or heating and the monomer feed may or may not be refrigerated.See the disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, International Patent Publication Nos. WO 96/33227and WO 97/22639.

This invention also relates to:

1. A fluorophenylborate represented by the formula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻where Ct⁺ is a cation capable of extracting an alkyl group from, orbreaking a carbon-metal bond of, an organo metallic compound; Ar^(f) isa fluorophenyl group; n is 1 or 2; and each R is independently selectedfrom a fluorophenyl group and a fluoronaphthyl group, provided that whenn=1, each R group is connected at the 3-position relative the connectionbetween the associated Ar^(f) group and the boron atom and, when n=2;the R groups are connected at the 3-position and the 5-positionrespectively relative the connection between the associated Ar^(f) groupand the boron atom.2. The fluorophenylborate of paragraph 1 wherein each R is independentlyselected from a perfluorophenyl group and a perfluoronaphthyl group.3. The fluorophenylborate of paragraph 1 or 2 wherein each Ar^(f) is aperfluorophenyl group.4. The fluorophenylborate of paragraph 1, 2 or 3 wherein Ct⁺ is selectedfrom silylium, trityl carbenium, Group-12 metal, anilinium, ammonium,phosphonium, and arsonium cations, and anilinium, ammonium, phosphonium,and arsonium cationic derivatives wherein the cationic derivativescontain C₁ to C₈ hydrocarbyl, hydrocarbylsilyl, or hydrocarbyl-aminesubstituents for one or more cation hydrogen atoms.5. The fluorophenylborate of any of paragraphs 1 to 4 wherein Ct⁺ is a[4-t-butyl-N,N-dimethylanilinium] cation.6. The fluorophenylborate of paragraphs 1 to 5 and comprising an anionselected from (meta-C₆F₅—C₆F₄)₄B⁻ and 3,5-(C₆F₅)₂—C₆F₃)₄B⁻.7. An olefin polymerization catalyst system comprising a (a) a catalystprecursor comprising an organometallic compound and (b) an activatorcomprising a compound represented by the formula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻where Ct⁺ is a cation capable of extracting an alkyl group from, orbreaking a carbon-metal bond of, an organo metallic compound; Ar^(f) isa fluorophenyl group; n is 1 or 2; and each R is independently selectedfrom a fluorophenyl group and a fluoronaphthyl group, provided that whenn=1, each R group is connected at the 3-position relative the connectionbetween the associated Ar^(f) group and the boron atom and, when n=2;the R groups are connected at the 3-position and the 5-positionrespectively relative the connection between the associated Ar^(f) groupand the boron atom.8. The catalyst system of paragraph 7 wherein each R is independentlyselected from a perfluorophenyl group and a perfluoronaphthyl group.9. The catalyst system of paragraph 7 or 8 wherein each Ar^(f) is aperfluorophenyl group.10. The catalyst system of paragraph 7, 8, or 9 wherein Ct⁺ is selectedfrom silylium, trityl carbenium, Group 12 metal, anilinium, ammonium,phosphonium, and arsonium cations, and anilinium, ammonium, phosphonium,and arsonium cationic derivatives wherein the cationic derivativescontain C₁ to C₈ hydrocarbyl, hydrocarbylsilyl, or hydrocarbyl-aminesubstituents for one or more cation hydrogen atoms.11. The catalyst system of paragraph 7, 8, 9, or 10 wherein Ct⁺ is a[4-t-butyl-N,N-dimethylanilinium] cation.12. The catalyst system of paragraph 7, 8, 9, 10, or 11 wherein saidactivator (b) comprises an anion selected from (meta-C₆F₅—C₆F₄)₄B⁻and3,5-(C₆F₅)₂—C₆F₃)₄B⁻.13. The catalyst system of paragraph 7, 8, 9, 10, 11, or 12 wherein saidcatalyst precursor is selected from a metallocene catalyst precursor, abisamide catalyst precursor, an amine bisamide catalyst precursor, or apyridine bisamide catalyst precursor.14. The catalyst system of paragraph 7, 8, 9, 10, 11, 12, or 13 whereinthe catalyst precursor (a) and the activator (b) are present in a ratioof about 10:1 to about 1:10.15. The catalyst system of paragraph 7, 8, 9, 10, 11, 12, 13, or 14wherein the catalyst precursor (a) and the activator (b) are present ina ratio of about 5:1 to about 1:5.16. The catalyst system of any of paragraphs 7 to 15 wherein thecatalyst precursor (a) and the activator (b) are present in a ratio ofabout 2:1 to about 1:2.17. The catalyst system of any of paragraphs 7 to 16 and furtherincluding a porous support.

18. A process for polymerizing at least one olefin monomer comprisingcontacting said monomer with the catalyst system of any of paragraphs 1to 17.

19. The process of paragraph 18 wherein said olefin monomer comprises atleast one of a C₂ to C₃₀ olefin, a C₄ to C₃₀ diolefin, C₇ to C₃₀ vinylaromatic monomer and a C₅ to C₂₀ cyclic olefin.

The process of pargraph 18 wherein said olefin monomer comprisesethylene and/or propylene.

The invention will now be more particularly described with reference tothe following non-limiting Examples.

ACTIVATOR SYNTHESIS EXAMPLES Example 1 Synthesis of3-Bromotetrafluorobenzene

To a cold (−78° C.) solution of 3,5-tetrabromobenzene (19 grams) indiethyl ether (Et₂O) was added BuLi (10 ml, 1.6 M, Aldrich). After 1hour of reaction time, the mixture was quenched with an HCl(aq)/Et₂Omixture and allowed to reach room temperature. The organic layer wasseparated and dried with MgS0₄. The solvent was removed and the productpurified by distillation (b.p. 130-135° C., 10.01 grams). ¹⁹F NMR (25°C., CDCl₃, referenced with CFCl₃) −190.4 (t, 1F), −124.7(m, 1F),−132.6(m, 1F), −162.2(m, 1F).

Example 2 Synthesis of 3-pentafluorophenyl-2,4,5,6-tetrafluorobenzene

To a toluene/tetrahydrofuran solution of the 3-bromotetrafluorobenzene(6 grams) produced in Example 1 was added (C₆F₅)₂Cu-dioxane (13 grams)and the mixture was refluxed for 2 days. After an aqueous work-up, theorganic layer was separated, and the solvent removed. The residualmaterial was sublimed and the sublimate was passed through a silicacolumn (hexanes). The yield was 5.3 grams. ¹⁹F NMR (25° C., CDCl₃,referenced with CFCl₃): −114.0 (m, 1F), −128.6 (m, 1F), −130.5 (m, 1F),−138.4(m, 2F), −151.7 (t, 1F), −161.7 (m, 2F), −164.0 (m, 1 F).

Example 3 Synthesis of [4-tBu-PhNMe₂H][(m-C₆F₅—C₆F₄)₄B]

The biphenyl prepared Example 2 was used to make the correspondingborate using standard methodology. To a cold solution of m-C₆F₅—C₆F₄H(1.5 grams) in diethylether was added 1 equivalent of BuLi (1.6 M,Aldrich). The reaction was allowed to stir at −78° C. for 1 hour andthen a hexane solution of BCl₃ (¼equivalent) was added. The ice bath wasremoved and the reaction mixture was stirred for 3 hours. The solventwas replaced with methylene chloride, and the LiCl byproduct removed. Anoily material was obtained after the solvent was removed. Saltmetathesis with 4-tBu-PhNMe₂HCl was performed using the oily material,and the LiCl byproduct removed by filtration. The solvent was removedunder vacuum. The resulting white product was collected. Yield: 1.53grams. ¹⁹F NMR: −105.5 (bm, 4F), −123.6 (bm, 4F), −139.2 (bm, 8F),−141.5 (bm, 4F), −155.2 (bm, 4F), −163.7 (bm 8F), −169.7 (bm, 4F).

Example 4 Synthesis of 1,3,5-tribromotrifluorobenzene

To a suspension of iron in 1,3,5-trifluorobenzene (40 grams) was addedBr₂ through a dropping funnel. After the addition was complete, thereaction mixture was refluxed for 16 hours. The mixture was thenquenched with an aqueous hydrogen bisulfate solution, and the productextracted with methylene chloride. The organic layer was separated anddried with MgS0₄. After filtration, the solvent was removed, leaving awhite crystalline material. Yield: 65 grams. ¹⁹F NMR (25° C., CDCl₃)−95.9(s).

Example 5 Synthesis of 3,5-dibromotrifluorobenzene

22.363 grams of the Br₃F₃C₆ produced in Example 4 was dissolved intetrahydrofuran and, after cooling the resultant solution with an icebath to −5° C., 1 equivalent of EtMgBr (Et₂O, Aldrich) was added. Awhite precipitate appeared after the addition was complete. Afterstirring the reaction mixture for 1 hour, the ice bath was removed andthe temperature was allowed to reach 25° C. After an aqueous work-up,the solvent was evaporated to produce a colorless semisolid material.Yield 10.34 grams. ¹⁹F NMR (25° C., CDCl₃) −98.5 (s, 1F), −106.4 (m,2F).

Example 6 Synthesis of 3,5-bis(pentafluorophenyl)trifluorobenzene

To a toluene/tetrahydrofuran solution of the 3,5-dibromotrifluorobenzene(7.645 grams) produced in Example 5 was added (C₆F₅)₂Cu-dioxane (40.0grams). The mixture was refluxed for 2 days. After an aqueous work-up,the organic layer was separated, and the solvent removed. The residualmaterial was purified by recrystallization from hexane. The product wascollected by filtration. Yield 9.64 grams. ¹⁹F NMR (25° C., CDCl₃,referenced with CFCl₃) −103.9 (s, 2F), −106.3 (s, 1F), −138.1 (m, 4F),−151.5 (t, 2F), −161.5 (m, 4F).

Example 7 Bromination of 3,5-bis(pentafluorophenyl)trifluorobenzene

To a mixture of 3,5-bis(pentafluorophenyl)trifluorobenzene (7.55 grams)produced in Example 6 and iron powder was added Br₂. The mixture wasrefluxed for 3 days. After quenching the Br₂ and extracting the productwith methylene chloride, the organic layer was dried with MgS0₄. Afterfiltering off the drying agent, the solvent was replaced with hexane.Recrystallization afforded the product (5.701 grams) as a whitecrystalline material.

Example 8 Synthesis of [Li(Et₂O_(2.5)][(3,5-(C₆F₅)₂—C₆F₃)₄B]

To a cold solution of 1-bromo-3,5-bis(pentafluorophenyl)trifluorobenzene(5.188 grams) produced in Example 7 was added 1 equivalent of BuLi(1.6M, Aldrich). After 35 minutes, BCl₃ was added. The mixture wasstirred for 40 minutes, then allowed to reach room temperature, andstirred for an additional 1 hour. The solvent was replaced withmethylene chloride and the LiCl removed by filtration using celite.Following partial evaporation, pentane was added to induceprecipitation. The mixture was chilled, before the product was collectedby filtration. A final pentane wash provided the product as a whitesolid (3.761 grams). ¹⁹F NMR (25° C., CDCl₃, referenced with CFCl₃)−95.8 (s, 8F), −118.1 (s, 4F), −139.3 (m, 16F), −155.9 (t, 8F), −164.3(m, 16F).

Example 9 Synthesis of [4-tBuPhNMe₂H][(3,5-(C₆F₅)₂—C₆F₃)₄B]

3.651 grams of [Li(Et₂O_(2.5)][(3,5-(C₆F₅)₂—C₆F₃)₄B] produced in Example8 were dissolved in methylene chloride and was stirred with a methylenechloride solution of 4-tBuPhNMe₂HCl for 45 minutes. The LiCl by-productwas removed by filtration. The solvent was replaced with toluene, andpentane added to incipient cloudiness. After chilling the mixture at−35° C., the product was collected by filtration and washed withpentane. The residual solvent was removed by placing the product underhigh vacuum while heating to 110° C. for 4.5 hours. ¹⁹F NMR (same asExample 3) indicated pure product. Yield: 3.401 grams.

POLYMERIZATION EXAMPLES

A series of ethylene-alpha-olefin copolymerizations were performed using1-octene as the comonomer and a number of different metallocenecatalysts and fluorophenyl and fluoronaphthyl borate activators. Theresults are reported in Table 1 below.

The activators included the products of Examples 3 and 9 labeled D andB, respectively, in the structural formulae and two conventional borateactivators, namely [4-tBuPhNMe₂H][(C₁₀F₇)₄B] labeled A in the structuralformulae below and [4-tBuPhNMe₂H][(C₆F₅)₄B] labeled C in the structuralformulae below.

The metallocene catalysts employed included the materials labeled E, F,G, and H in the structural formulae below:

E=bis(para-triethylsilylphenyl)methylene (cyclopentadienyl)(2,7-ditertbutyl-fluorenyl)hafnium dimethyl;

F=dimethylsilyl(bis-indenyl)hafnium dimethyl;

G=dimethylsilyl(tetramethycyclopentadienyl) (cyclooctylamido)titaniumdimethyl; and

H=bis(phenyl)methylene(cyclopentadienyl) (fluorenyl)hafnium dimethyl.

Each polymerization test was run in a glass-lined 5-milliliter autoclavereactor equipped with a mechanical stirrer, an external heater fortemperature control, a septum inlet and a regulated supply of drynitrogen and ethylene in an inert atmosphere (nitrogen) glove box. Thereactor was dried and degassed thoroughly at 115° C. A diluent,comonomer, and scavenger, were added at room temperature and atmosphericpressure. The reactor was then brought to process pressure and chargedwith ethylene while stirring at 800 RPM. The activator and catalyst wereadded via syringe with the reactor at process conditions. Thepolymerization was continued while maintaining the reaction vesselwithin 3° C. of the target process temperature and 5 psig (34 kPa) oftarget process pressure (by automatic addition of ethylene on demand)until a fixed uptake of ethylene was noted (corresponding to ca. 0.15 gpolymer) or until a maximum reaction time of 20 minutes had passed. Thereaction was stopped by pressurizing the reactor to 30 psig (207 kPa)above the target process pressure with a gas mixture composed of 5 mol %oxygen in argon. The polymer was recovered by vacuum centrifugation ofthe reaction mixture. Bulk polymerization activity was calculated bydividing the yield of polymer by the total weight of the catalyst chargeby the time in hours and by the absolute monomer pressure inatmospheres. The specific polymerization activity was calculated bydividing the yield of polymer by the total number of millimoles oftransition metal contained in the catalyst charge by the time in hoursand by the absolute monomer pressure in atmospheres. TABLE 1 ActivatorCatalyst % Octene Mw Mn QT(a) Yield(b) Act(c) A E 30.8 873326 459306306.9 0.209 163352 B E 26.8 1227178 389298 138.7 0.194 335886 C E 32.6941435 359464 158.9 0.206 310403 A E 27.8 1277730 564718 222.6 0.204219838 B E 27.9 1306600 380611 135.2 0.182 323883 C E 28.4 917325 318875130.9 0.203 371911 A F 24.9 538394 322048 36.7 0.113 736698 B F 27.5345581 136350 29.6 0.184 1495135 C F 25.6 388091 231445 29.5 0.102831707 A F 24.7 519868 305263 38.4 0.124 776067 B F 27.2 331338 12676223.4 0.181 1862671 C F 25.8 317877 183436 25.1 0.112 1066135 A G 32.8529095 248672 54.7 0.155 680132 B G 34.0 727898 199555 61.9 0.183 708686C G 29.2 481970 236278 36.7 0.153 996843 A G 29.8 541922 249355 53.10.154 697270 B G 22.5 678695 224801 48.7 0.176 864847 C G 11.6 393259173766 35.2 0.164 1118910 A H 27.8 1281727 770214 63.4 0.094 353776 B H28.0 1017740 371580 133.2 0.169 304347 C H 26.9 1197383 733800 94.60.091 231325 A H 28.0 1330405 793966 75.3 0.105 334528 B H 26.4 1005842367618 45.7 0.166 871582 C H 27.1 985666 552501 78.3 0.121 369655 A E31.9 1139206 528162 159.6 0.165 247669 B E 27.7 1297955 369483 121.40.184 363756 C E 31.3 1077142 391479 137.5 0.194 338370 A E 27.5 1406540605749 143.3 0.164 275281 B E 26.5 1261551 399811 95.8 0.176 441031 C E32.4 1013757 489391 39.9 0.151 909100 A F 23.1 542482 324864 33.8 0.108767830 B F 25.1 382211 157275 23.4 0.172 1756247 C F 26.6 336457 19318826.6 0.106 955664 A F 7.9 648240 338164 7.4 0.032 1044898 B F 20.3326268 153321 146.1 0.374 614538 C F 25.3 335501 194869 5.7 0.0933880139 A G 33.6 632428 290031 54.6 0.148 649350 B G 35.0 833868 27688759.3 0.155 626298 C G 30.5 503336 248427 34.0 0.136 959154 A G 34.0631606 329913 45.7 0.144 755517 B G 32.8 885361 400882 66.6 0.144 517167C G 35.5 470821 231047 32.5 0.144 1064290 A H 26.7 1513491 945792 96.20.086 213555 B H 24.1 1080331 451270 35.3 0.150 1020034 C H 26.8 1503997965301 94.5 0.064 162979 A H 28.3 1416014 905129 62.1 0.101 391750 B H22.6 1196811 566381 76.8 0.140 438666 C H 25.4 853983 434098 59.0 0.102416684 A E 29.4 1739067 1171641 361.2 0.156 77845 D E 34.5 791000 203509140.0 0.222 285604 C E 30.9 880288 324780 164.3 0.211 231067 A E 27.11114124 377003 155.4 0.202 233569 D E 29.1 891463 303781 163.8 0.210231127 C E 32.0 826184 262797 131.7 0.212 289974 A F 28.9 434332 24759027.9 0.140 904519 D F 29.7 223643 111971 19.2 0.155 1453846 C F 27.2266119 143140 20.4 0.139 1219667 A F 26.8 479632 286466 35.7 0.130656287 D F 29.5 245276 130613 20.6 0.146 1274128 C F 25.8 326288 20392628.0 0.100 641387 A G 28.9 497448 226962 51.7 0.163 568458 D G 26.5407860 166429 49.1 0.184 673120 C G 35.9 388306 155568 30.8 0.162 947030A G 30.7 516519 224971 50.4 0.162 577513 D G 34.0 651541 551572 45.60.173 682201 C G 31.5 424935 202725 35.3 0.148 751995 A H 27.8 933784508402 112.1 0.136 217612 D H 32.1 705849 324346 107.7 0.157 262970 C H32.6 923314 509265 84.3 0.110 234987 A H 30.1 1008994 589812 115.3 0.129200642 D H 30.0 683608 292334 48.7 0.167 615887 C H 26.3 968278 553254101.2 0.122 217794 A E 26.6 1113206 376594 130.6 0.190 261139 D E 25.8812604 260344 131.5 0.206 281537 C E 33.9 830389 288859 51.6 0.202704863 A E 29.5 1086331 451706 71.6 0.173 435670 D E 33.9 754390 26792688.7 0.205 416462 C E 31.3 864963 302902 107.7 0.198 330875 A F 27.2440115 250287 24.9 0.140 1012953 D F 26.0 220341 107690 19.2 0.1521427263 C F 25.7 266261 140377 19.1 0.135 1275079 A F 27.6 428823 25045226.8 0.123 826119 D F 27.3 260176 139289 30.7 0.154 903520 C F 27.1275397 154858 22.2 0.126 1025553 A G 36.3 575980 222526 48.5 0.170630538 D G 28.1 462870 213858 33.7 0.159 846902 C G 35.6 450127 22767333.8 0.145 770668 A G 30.3 541348 243450 47.2 0.160 609413 D G 25.5423513 169533 33.7 0.173 923747 C G 33.6 452305 215879 34.1 0.156 825330A H 27.5 1169360 662620 102.2 0.129 226475 D H 33.0 698392 279906 51.90.172 598033 C H 27.9 838232 408637 50.6 0.148 526543 A H 30.8 1133963694364 56.3 0.118 375733 D H 30.1 765102 339351 41.4 0.157 682234 C H28.5 841879 438440 54.6 0.135 446619(a)QT = Quench Time (sec);(b)grams;(c)Act = activity in grams of polymer/(mmol hour).

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

1. A fluorophenylborate represented by the formula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻ where Ct⁺ is a cation capable of extracting analkyl group from, or breaking a carbon-metal bond of, an organo metalliccompound; Ar^(f) is a fluorophenyl group; n is 1 or 2; and each R isindependently selected from a fluorophenyl group and a fluoronaphthylgroup, provided that when n=1, each R group is connected at the3-position relative the connection between the associated Ar^(f) groupand the boron atom and, when n=2; the R groups are connected at the3-position and the 5-position respectively relative the connectionbetween the associated Ar^(f) group and the boron atom.
 2. Thefluorophenylborate of claim 1 wherein each R is independently selectedfrom a perfluorophenyl group and a perfluoronaphthyl group.
 3. Thefluorophenylborate of claim 1 wherein each Ar^(f) is a perfluorophenylgroup.
 4. The fluorophenylborate of claim 1 wherein Ct⁺ is selected fromsilylium, trityl carbenium, Group-12 metal, anilinium, ammonium,phosphonium, and arsonium cations, and anilinium, ammonium, phosphonium,and arsonium cationic derivatives wherein the cationic derivativescontain C₁ to C₈ hydrocarbyl, hydrocarbylsilyl, or hydrocarbyl-aminesubstituents for one or more cation hydrogen atoms.
 5. Thefluorophenylborate of claim 1 wherein Ct⁺ is a[4-t-butyl-N,N-dimethylanilinium] cation.
 6. The fluorophenylborate ofclaim 1 and comprising an anion selected from (meta-C₆F₅—C₆F₄)₄B⁻ and3,5-(C₆F₅)₂—C₆F₃)₄B⁻.
 7. An olefin polymerization catalyst systemcomprising a (a) a catalyst precursor comprising an organometalliccompound and (b) an activator comprising a compound represented by theformula:Ct⁺[B—(Ar^(f)R_(n))₄]⁻ where Ct⁺ is a cation capable of extracting analkyl group from, or breaking a carbon-metal bond of, an organo metalliccompound; Ar^(f) is a fluorophenyl group; n is 1 or 2; and each R isindependently selected from a fluorophenyl group and a fluoronaphthylgroup, provided that when n=1, each R group is connected at the3-position relative the connection between the associated Ar^(f) groupand the boron atom and, when n=2; the R groups are connected at the3-position and the 5-position respectively relative the connectionbetween the associated Ar^(f) group and the boron atom.
 8. The catalystsystem of claim 7 wherein each R is independently selected from aperfluorophenyl group and a perfluoronaphthyl group.
 9. The catalystsystem of claim 7 wherein each Ar^(f) is a perfluorophenyl group. 10.The catalyst system of claim 7 wherein Ct⁺ is selected from silylium,trityl carbenium, Group 12 metal, anilinium, ammonium, phosphonium, andarsonium cations, and anilinium, ammonium, phosphonium, and arsoniumcationic derivatives wherein the cationic derivatives contain C₁ to C₈hydrocarbyl, hydrocarbylsilyl, or hydrocarbyl-amine substituents for oneor more cation hydrogen atoms.
 11. The catalyst system of claim 7wherein Ct⁺ is a [4-t-butyl-N,N-dimethylanilinium] cation.
 12. Thecatalyst system of claim 7 wherein said activator (b) comprises an anionselected from (meta-C₆F₅—C₆F₄)₄B⁻ and 3,5-(C₆F₅)₂—C₆F₃)₄B⁻.
 13. Thecatalyst system of claim 7 wherein said catalyst precursor is selectedfrom a metallocene catalyst precursor, a bisamide catalyst precursor, anamine bisamide catalyst precursor, or a pyridine bisamide catalystprecursor.
 14. The catalyst system of claim 7 wherein the catalystprecursor (a) and the activator (b) are present in a ratio of about 10:1to about 1:10.
 15. The catalyst system of claim 7 wherein the catalystprecursor (a) and the activator (b) are present in a ratio of about 5:1to about 1:5.
 16. The catalyst system of claim 7 wherein the catalystprecursor (a) and the activator (b) are present in a ratio of about 2:1to about 1:2.
 17. The catalyst system of claim 7 and further including aporous support.
 18. A process for polymerizing at least one olefinmonomer comprising contacting said monomer with the catalyst system ofclaim
 7. 19. The process of claim 18 wherein said olefin monomercomprises at least one of a C₂ to C₃₀ olefin, a C₄ to C₃₀ diolefin, C₇to C₃₀ vinyl aromatic monomer and a C₅ to C₂₀ cyclic olefin.
 20. Theprocess of claim 18 wherein said olefin monomer comprises ethyleneand/or propylene.